CN103011189A - Microporous-mesoporous molecular sieve containing noble metal, preparation method and application to catalytic reduction of p-nitrophenol - Google Patents
Microporous-mesoporous molecular sieve containing noble metal, preparation method and application to catalytic reduction of p-nitrophenol Download PDFInfo
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Abstract
The invention belongs to the technical field of molecular sieve preparation, and particularly relates to an in-situ preparation method for a microporous-mesoporous molecular sieve containing noble metal. The in-situ preparation method comprises the steps as follows: adding a coupling pore-forming agent, a silicon source, an aluminum source or a titanium source, and an alkali source into a water solution of noble metal nano particles in sequence under the water bath condition; and ageing, drying, crystallizing, drying and carrying out high-temperature calcination to obtain the microporous-mesoporous molecular sieve containing the noble metal. The prepared microporous-mesoporous molecular sieve is provided with a hierarchical pore structure; the noble metal nano particles with high dispersity are covered in situ while a mesoporous structure is generated; and a synthetic method is convenient and simple, saves energy and reduces emission. A multifunctional catalyst prepared with the method integrates the advantages of the microporous channels of the molecular sieve, the transgranular meso pores and the intergranular meso pores of the molecular sieve and the noble metal nano particles, and is more suitable for catalytic reactions of sulfur-containing large molecules such as hydrogen desulfurization and the like.
Description
Technical field
The invention belongs to the molecular sieve technical field, be specifically related to a kind of in-situ preparation method that contains the micropore-mesopore molecular sieve of precious metal.
Background technology
Micro porous molecular sieve is as a series of crystal microporous aluminosilicates material, because its intrinsic structural performance makes it be widely used in catalysis, fractionation by adsorption field and environmental area such as the nano level duct of larger specific surface area, rule, the micropore hole wall of height crystallization and adjustable hole wall composition.Yet, microporous molecular sieve catalyst because its less aperture (＜1.5nm), limited greatly large size reactant and the diffusion of product in its duct, seriously reduced the utilising efficiency of catalyzer, especially in the application in the fields such as the upgrading of crude oil and fine chemistry industry.In order to address this problem, in recent years, a kind of material that integrates the advantages such as high diffusibility of micro porous molecular sieve high catalytic activity, thermostability and mesopore molecular sieve, namely the micropore-mesopore molecular screen material becomes the most effective way that overcomes above-mentioned shortcoming.
Hydrogenation and hydrogenating desulfurization (HDS) reaction is the important reaction that improves gasoline and diesel quality in the oil refining industry, and particularly along with the requirement of countries in the world legislation to the oil product sulphur content improves gradually, the importance of hydrodesulfurization reaction also manifests day by day.The catalyzer of conventional hydrodesulfurization reaction is γ-Al
2O
3Support precious metal, but γ-Al
2O
3Specific surface area less, be unfavorable for the dispersion of precious metal, simultaneously γ-Al
2O
3Acidity a little less than, bad for the synergistic action effect of noble metal catalyst.In catalyzed reaction, the micropore-mesopore molecular sieve is not only the important acid catalyst of a class, and its peculiar property is also so that it becomes the suitable support of the catalyst of a class, thus the structure dual-function catalyst.Therefore, the synthetic preparation of the success of micropore-mesopore molecular sieve is for Hydrobon catalyst provides novel carrier.
At present, people have been developed some and prepared the method for dual-function catalyst: at first, dipping-heat treating method is the most frequently used strategies of people.At first the multi-stage porous molecular sieve carrier is impregnated in the metal salt solution, subsequently by thermal treatment and H
2Reduction obtains metal nanoparticle.This preparation method's simple and effective is the effective ways of scale operation catalyzer, yet the method complex steps and being unfavorable for obtains to have the metal nanoparticle that single size distributes.Secondly, people also attempt adding the molecular screen material that the metal ion preparation contains metal nanoparticle in the synthetic precursor liquid of molecular sieve.But the noble metal of the method is easily assembled, and is difficult to control the dispersity of metallics.Another kind method is that noble metal nano particles with pre-synthesis is with molecular sieve precursor liquid together embedding in situ.For example, and the report of Christensen (Angew.Chem., Int.Ed.2012,49,3504-3507), use a kind of silane coupled pore-forming material that contains thiol group that noble metal Au nanoparticle step in hydro-thermal reaction system is supported in the molecular sieve crystal.Although the method is simple, the organosilane of its use is more special, sucks toxic to health; Synthetic cost is higher; And can emit the sulfur dioxide pollution atmosphere after the high-temperature calcination.In addition, the prepared material shortage of the method is conducive to the mesoporous passage of large size reaction species contact noble metal active position.
Summary of the invention
The object of the invention is to use the coupling pore-forming material of biological nontoxic or low toxicity, by the synthetic micropore-mesopore molecular sieve that contains noble metal of single stage method.The synthetic micropore-mesopore molecular sieve of this method has hierarchical porous structure, and when generating meso-hole structure, original position has coated the noble metal nano particles of high degree of dispersion, and synthetic method is convenient, simple, energy-saving and emission-reduction.The prepared polyfunctional catalyst of the method has compiled the advantage of the mesoporous and noble metal nano particles of the intracrystalline intergranular mesoporous and molecular sieve of micropore canals, molecular sieve of molecular sieve, and it is more suitable in catalyzed reactions such as macromolecular hydroisomerizing, the macromolecular hydrogenating desulfurizations of sulfur-bearing.
A kind of micropore-mesopore molecular screen material that contains precious metal of the present invention has following characteristic feature: material have simultaneously the aperture less than the micropore canals of 2nm scope and aperture at the mesopore orbit of 2～50nm scope, namely possess hierarchical porous structure.Its skeleton consists of the pure silicon molecular screen material, or the silica-based molecular screen material of metal A l, Ti doping; Active noble metals nanoparticle high dispersing is in mesopore orbit.This material has been showed good and stable catalytic activity in the catalytic reduction reaction of p-NP.SiO
2, Al
2O
3Or TiO
2, noble metal source mol ratio be 100:0～25:0.1～5.
A kind of in-situ preparation method that contains the micropore-mesopore molecular sieve of precious metal of the present invention, its step is as follows:
1) under water bath condition, in the aqueous solution of noble metal nano particles, add successively the coupling pore-forming material, the silicon source, aluminium source or titanium source, alkali source is stirred to the formation collosol and gel; Wherein the mol ratio of silicon source, aluminium source or titanium source, alkali source, noble metal source, coupling pore-forming material, water is 100:0～25:10～40:0.1～5:0.1～5:500～1500, and the silicon source is with SiO
2Meter, the aluminium source is with Al
2O
3Meter, the titanium source is with TiO
2Meter, noble metal source is in precious metal simple substance;
2) with prepared collosol and gel ageing certain hour at a certain temperature;
3) dry for some time obtains dried glue at a certain temperature with the collosol and gel after the ageing;
4) dried glue is transferred in the reactor, by the method for steam auxiliary phase transformation (SAC), at a certain temperature crystallization for some time;
5) product after the crystallization repeatedly washs, dries through water and ethanol, and template is removed in the final high temperature calcining, thereby obtains the micropore-mesopore molecular sieve.
Further, the bath temperature described in the step 1) is 25 ° of C～80 ° C, is preferably 40 ° of C.
Step 2) Aging Temperature of stating in is 25 ° of C～100 ° C, and digestion time is 2～24 hours, preferably 60 ° of C ageings 12 hours.Ageing stage can further strengthen the mutual polycondensation of collosol and gel internal reaction species, makes more homogeneous of system.It is lower that Aging Temperature is crossed when low productive rate, and by product was more when Aging Temperature was too high.
Drying temperature described in the step 3) is 25 ° of C～100 ° C, and be 0.5～24 hour time of drying, preferably dry 12 hours of 80 ° of C.
Crystallization temperature described in the step 4) is 100 ° of C～200 ° C, and crystallization time is 6 hours～240 hours.Preferably 160 ° of C crystallization 24 hours.
Bake out temperature described in the step 5) is 100～120 ° of C, and drying time is 10～20 hours; The temperature rise rate of calcining is 1～2 ° of C/min, and calcining temperature is 500～650 ° of C, and calcination time is 6～24 hours.
In the aforesaid method, described noble metal nano particles is the alloy of one or more precious metals in the precious metals such as Pt, Ru, Rh, Pd, Re, Os, Ir, Ag and Au.
Described silicon source is methyl silicate, tetraethoxy, white carbon black, water glass, silicon sol etc.
Described aluminium source is pseudo-boehmite, aluminum isopropylate, aluminum nitrate, Tai-Ace S 150, aluminium sesquioxide, aluminum chloride, aluminium hydroxide etc.
Described titanium source is tetra-n-butyl titanate, titanium isopropylate, tetraethyl titanate, titanium tetrachloride, titanium sulfate, titanium valve etc.
Described alkali source is inorganic alkali source or organic alkali source.Inorganic alkali source is the oxyhydroxide of basic metal or alkaline-earth metal, alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide etc., the oxyhydroxide of alkaline-earth metal such as magnesium hydroxide, calcium hydroxide etc.Organic alkali source is urea, quaternary ammonium hydroxide compounds, fat amine compound, alcamine compound or the mixture that is comprised of them.
The general formula of quaternary ammonium hydroxide compounds is (R
1)
4NOH, R
1For having the alkyl of 1～4 carbon atom, preferred alkyl is propyl group.
The general formula of fat amine compound is R
2(NH
2)
n, R
2Be selected from alkyl or alkylidene group with 1～6 carbon atom, n=1 or 2; Be preferably ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
The general formula of alcamine compound is (HOR
3)
mNH
(3-m), R
3Be selected from the alkyl with 1～4 carbon atom, m=1,2 or 3; Be preferably monoethanolamine, diethanolamine or trolamine.
The prepared micropore-mesopore molecular sieve of the present invention comprises MFI(silicalite-1, ZSM-5 molecular sieve), the FAU(X type, Y zeolite), the BEA(beta molecular sieve), MOR, LTA(NaA molecular sieve), the LTL(L molecular sieve), SOD, GIS, OFF, ZSM-2, MTN, AEL etc.
In the aforesaid method, described coupling pore-forming material refers to polymkeric substance or tensio-active agent.
Described polymkeric substance is glucose for example, cyclodextrin, polybenzimidazole, chitosan, polypropylene, polyoxyethylene glycol, polystyrene, polyvinyl chloride, polyethylene, the derivative of the polymkeric substance such as methylcellulose gum and polymkeric substance, pyrrolidone such as polymkeric substance, vinyl alcohol, ether, the derivatives such as pyrimidine are such as polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ethyl ether, the polyethylene pyrimidine, the polybenzimidazole pyrrolidone, polybenzimidazole alcohol, the polybenzimidazole ether, the polybenzimidazole pyrimidine, the polypropylene pyrrolidone, POLYPROPYLENE GLYCOL, the polypropylene ether, the polypropylene pyrimidine, the polyoxyethylene glycol pyrrolidone, the polyoxyethylene glycol ether, the polyoxyethylene glycol pyrimidine, the polystyrene pyrrolidone, polystyrene alcohol, the polystyrene ether, the polystyrene pyrimidine, the polyvinyl chloride pyrrolidone, polyvinyl chloride alcohol, the polyvinyl chloride ether, the polyvinyl chloride pyrimidine, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ethyl ether and polyethylene pyrimidine etc.
Described tensio-active agent can be anion surfactant, cats product or nonionogenic tenside.
Anion surfactant is soap, sulfuric acid, phosphate ester salt, alkylbenzene sulfonate, sulfonated α-olefin, alkylsulfonate, alpha-sulfo monocarboxylate, lipid acid sulfoalkyl ester, sulphosuccinates, sulfonated alkyl naphathalene, sulfonated petro-leum, sulfonated lignin, alkyl glyceryl ether sulfonate etc.
Cats product is fatty amines quaternary cationics, ring-type cats product, as: cetyl trimethylammonium bromide, dimethyl dodecyl amine oxide, three sufferings (ninth of the ten Heavenly Stems) ylmethyl chlorine (bromine) are changed ammonium etc.
Nonionogenic tenside is fatty alcohol-polyoxyethylene ether, block polyoxyethylene polyoxypropylene ether (PluronicF127, Pluronic P123, Brij35, Brij56 etc.), alkylol amide, polyol ester class, tween series (Tween40, Tween60, Tween80 etc.), sapn series, fluorocarbon surfactant are serial.
The synthetic molecular sieve method that contains the noble metal nano particles multi-stage porous provided by the invention is compared with existing method has following advantage:
1. the preparation method who contains noble metal nano particles multi-stage porous molecular sieve that proposes of the present invention adopts low toxicity or nontoxic polymkeric substance or tensio-active agent, need not with more expensive hydrosulphonyl silane coupling pore-forming material, such as mercaptopropyl trimethoxysilane etc.; Reduce industrial cost and reduce calcining to the pollution of atmosphere.
2. the preparation method who contains noble metal nano particles multi-stage porous molecular sieve that proposes of the present invention, used the coupling pore-forming material, stable coating function between noble metal nano particles and the molecular sieve is improved, overcome the drawback that traditional dip loading method is assembled precious metal, the dispersiveness of precious metal is good especially, and this has guaranteed its activity.
3. the preparation method who contains noble metal nano particles multi-stage porous molecular sieve of the present invention's proposition can by the molecular weight of simple modulation coupling pore-forming material, effectively control the mesoporous aperture of multi-stage porous molecular sieve;
4. the preparation method who contains noble metal nano particles multi-stage porous molecular sieve that proposes of the present invention, can just can obtain having micropore (molecular sieve pore passage by high-temperature calcination in air, less than 2nm), it is mesoporous that (by the mesopore orbit of coupling pore-forming material structure, size is at the molecular sieve of 2～50nm) structures;
5. the sieve sample that contains the noble metal nano particles multi-stage porous that the present invention is prepared, a large amount of mesoporous existence are contained in inside, the second catalytic active component noble metal nano particles high dispersing makes its hydrodesulfurization reaction at large size thionaphthene and substituent molecule have great application prospect in its mesopore orbit simultaneously.
Description of drawings:
Fig. 1: be the powder X-ray RD spectrogram of the multi-stage porous sieve sample that contains noble metal nano particles of the embodiment of the invention 3 preparation;
The low power stereoscan photograph of the multi-stage porous molecular sieve that contains noble metal nano particles of Fig. 2: embodiment 3 preparations;
The high power stereoscan photograph of the multi-stage porous molecular sieve that contains noble metal nano particles of Fig. 3: embodiment 3 preparations;
The low power transmission electron microscope photo of the multi-stage porous molecular sieve that contains noble metal nano particles of Fig. 4: embodiment 3 preparations;
The high power transmission electron microscope photo of the multi-stage porous molecular sieve that contains noble metal nano particles of Fig. 5: embodiment 3 preparations;
The nitrogen adsorption desorption curve of the multi-stage porous molecular sieve that contains noble metal nano particles of Fig. 6: embodiment 3 preparations;
The mesoporous graph of pore diameter distribution of the multi-stage porous molecular sieve that contains noble metal nano particles of Fig. 7: embodiment 3 preparations.
The powder X-ray RD spectrogram of the multi-stage porous sieve sample that contains noble metal nano particles of Fig. 8: embodiment 2 preparations.
The powder X-ray RD spectrogram of the multi-stage porous sieve sample that contains noble metal nano particles of Fig. 9: embodiment 10 preparations.
The powder X-ray RD spectrogram of the multi-stage porous sieve sample that contains noble metal nano particles of Figure 10: embodiment 11 preparations.
The powder X-ray RD spectrogram of the multi-stage porous sieve sample that contains noble metal nano particles of Figure 11: embodiment 12 preparations.
The uv-vis spectra of the catalytic reduction tetranitro-phenol of the multi-stage porous molecular sieve that contains noble metal nano particles of Figure 12: embodiment 3 preparations;
As shown in Figure 1, the characteristic peak of the molecular sieve of the absorption peak of sample and MFI topological classification (Baerlocher C, McCusker L B, Olson D.Atlas of Zeolite Framework Types, 6th ed.[M] .Amsterdam:Elsevier, 2007.) very identical, prove that sample is the ZSM-5 molecular sieve with MFI type skeleton;
Shown in Fig. 2,3, the prepared molecular sieve that contains the noble metal nano particles multi-stage porous presents irregular spherical morphology, and has coarse surface tissue, and the molecular sieve particle diameter is greatly in 0.5～1.0 micrometer range;
Shown in Fig. 4,5, can be clearly seen that in molecular sieve crystal, there be the mesoporous passage of intracrystalline aperture in 2～10nm scope that the existence of this meso-hole structure is consistent with nitrogen adsorption result (Fig. 6); The a large amount of stains that distribute in the other crystal are precious metals pt nanoparticles, and this noble metal size is greatly about 5～6nm;
As shown in Figure 6, the nitrogen adsorption desorption curve of sample is at low nitrogen relative pressure (P/P
0＜0.02) high adsorption capacity the time has shown the existence of micropore in the sample; Further absorption in relative pressure is 0.4～0.9 scope, and have an obvious desorption hysteresis loop, illustrating has mesoporous existence in sample;
As shown in Figure 7, the mesoporous pore size distribution of sample is mainly about 2nm;
As shown in Figure 8, the characteristic peak of the molecular sieve of the absorption peak of sample and MFI topological classification (Baerlocher C, McCusker L B, Olson D.Atlas of Zeolite Framework Types, 6th ed.[M] .Amsterdam:Elsevier, 2007.) very identical, prove that sample is the silicalite-1 molecular sieve with MFI type skeleton;
As shown in Figure 9, the characteristic peak of the molecular sieve of the absorption peak of sample and BEA topological classification (Baerlocher C, McCusker L B, Olson D.Atlas of Zeolite Framework Types, 6th ed.[M] .Amsterdam:Elsevier, 2007.) very identical, prove that sample is the beta molecular sieve with BEA type skeleton;
As shown in figure 10, the characteristic peak of the molecular sieve of the absorption peak of sample and FAU topological classification (Baerlocher C, McCusker L B, Olson D.Atlas of Zeolite Framework Types, 6th ed.[M] .Amsterdam:Elsevier, 2007.) very identical, prove that sample is the X-type molecular sieve with FAU type skeleton;
As shown in figure 11, the characteristic peak of the molecular sieve of the absorption peak of sample and LTA topological classification (Baerlocher C, McCusker L B, Olson D.Atlas of Zeolite Framework Types, 6th ed.[M] .Amsterdam:Elsevier, 2007.) very identical, prove that sample is the A type molecular sieve with LTA type skeleton;
As shown in figure 12, can find out from its ultraviolet-visible absorption spectroscopy that the absorption peak of the p-NP that absorbs at 400nm constantly descends, be accompanied by the rising of absorption peak of the p-aminophenol of 300nm place absorption, the 15min afterreaction is complete.This result has shown that our prepared sample has excellent catalytic performance in the reduction reaction of p-NP.(the operating process of this experiment: p-NP (0.001M) solution of 0.15ml joined 1.5ml NaBH is housed
4(0.2M) in the quartz colorimetric utensil of solution, then add the 0.01g catalyzer, mixing solutions presents glassy yellow, and along with the carrying out of reaction, yellow is taken off gradually.In this process, follow the tracks of the reaction degree of carrying out in time by uv-vis spectra and change, until yellow completely dissolve).
Embodiment
The present invention will be further described below by embodiment, but embodiments of the present invention are not limited to this, can not be interpreted as limiting the scope of the invention.
Embodiment 1: the micropore-mesopore silicalite-1 molecular sieve that contains precious metals pt of synthetic pure silicon
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (polyvinylpyrrolidone), silicon source (tetraethyl orthosilicate), alkali source (TPAOH) is stirred to the formation collosol and gel; Wherein mole forms the silicon source: alkali source: platinum source: coupling pore-forming material: water=100:10:0.3:0.1:500, the silicon source is with SiO
2Meter, the platinum source is in Pt.Prepared collosol and gel is placed under 80 ° of C, the non-air tight condition dry 12 hours in 12 hours in ageing under 60 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 24 hours under the temperature of 160 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining removed template (TPAOH) and coupling pore-forming material (polyvinylpyrrolidone) in 15 hours, namely get the micropore-mesopore pure silicon silicalite-1 molecular sieve that contains precious metal 0.5wt.%Pt.
Embodiment 2: the micropore-mesopore silicalite-1 molecular sieve that contains precious metals pd of synthetic pure silicon
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pd nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (polyvinylpyrrolidone), silicon source (tetraethyl orthosilicate), alkali source (TPAOH) is stirred to the formation collosol and gel; Wherein mole forms the silicon source: alkali source: palladium source: coupling pore-forming material: water=100:10:0.3:0.2:1500, the silicon source is with SiO
2Meter, the palladium source is in Pd.Prepared collosol and gel is placed under 80 ° of C, the non-air tight condition dry 12 hours in 12 hours in ageing under 60 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 24 hours under the temperature of 160 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining removed template (TPAOH) and coupling pore-forming material (polyvinylpyrrolidone) in 15 hours, namely obtain structure with the micropore-mesopore pure silicon silicalite-1 molecular sieve that contains precious metal 0.5wt.%Pd among the embodiment 1.
Embodiment 3: the micropore-mesopore ZSM-5 molecular sieve that contains precious metals pt of synthesizing blender metal A l
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (polyvinylpyrrolidone), silicon source (tetraethyl orthosilicate), aluminium source (aluminum isopropylate), alkali source (TPAOH) is stirred to the formation collosol and gel; Wherein mole forms the silicon source: aluminium source: alkali source: platinum source: coupling pore-forming material: water=100:3:10:0.3:0.2:1500, the silicon source is with SiO
2Meter, the aluminium source is with Al
2O
3Meter, the platinum source is in Pt.Prepared collosol and gel is placed under 80 ° of C, the non-air tight condition dry 12 hours in 12 hours in ageing under 60 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 24 hours under the temperature of 160 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining removed template (TPAOH) and coupling pore-forming material (polyvinylpyrrolidone) in 15 hours, namely get the micropore-mesopore sial ZSM-5 molecular sieve that contains precious metal 0.5wt.%Pt.
Feed change proportioning (a, b, c, d) can obtain the Different Silicon aluminum ratio equally, and the micropore-mesopore sial ZSM-5 molecular sieve of different bullion contents.As shown in table 1.
Table 1: the micropore-mesopore ZSM-5 molecular sieve that contains precious metals pt of different mole silica alumina ratios
Embodiment 4: the micropore-mesopore TS-1 molecular sieve that contains precious metals pt of synthesizing blender metal Ti
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (polyvinylpyrrolidone), silicon source (tetraethyl orthosilicate), titanium source (tetrabutyl titanate), alkali source (TPAOH) is stirred to the formation collosol and gel; Wherein mole forms the silicon source: titanium source: alkali source: platinum source: coupling pore-forming material: water=100:2:10:0.3:0.2:1500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the platinum source is in Pt.。Prepared collosol and gel is placed under 80 ° of C, the non-air tight condition dry 12 hours in 12 hours in ageing under 60 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 2 days under the temperature of 180 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining removed template (TPAOH) and coupling pore-forming material (polyvinylpyrrolidone) in 15 hours, namely get the micropore-mesopore titanium silicon TS-1 molecular sieve that contains precious metal 0.5wt.%Pt.Embodiment 5: the micropore-mesopore TS-1 molecular sieve that contains precious metals pt of synthesizing blender metal Ti
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (polyvinylpyrrolidone), silicon source (tetraethyl orthosilicate), titanium source (titanium tetrachloride), alkali source (TPAOH) is stirred to the formation collosol and gel; Wherein mole forms the silicon source: titanium source: alkali source: platinum source: coupling pore-forming material: water=100:2:10:0.3:0.2:1500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the platinum source is in Pt.Prepared collosol and gel is placed under 80 ° of C, the non-air tight condition dry 12 hours in 12 hours in ageing under 60 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 2 days under the temperature of 180 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining removed template (TPAOH) and coupling pore-forming material (polyvinylpyrrolidone) in 15 hours, namely obtain the micropore-mesopore titanium silicon TS-1 molecular sieve that contains precious metal 0.5wt.%Pt with embodiment 4.
Embodiment 6:
Use cetyl trimethylammonium bromide (CTAB) to be the micropore-mesopore ZSM-5 molecular sieve that contains precious metals pt of coupling pore-forming material synthesizing blender metal A l.
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (cetyl trimethylammonium bromide), silicon source (tetraethyl orthosilicate), aluminium source (aluminum isopropylate), alkali source (TPAOH) is stirred to the formation collosol and gel; Wherein mole forms the silicon source: aluminium source: alkali source: platinum source: coupling pore-forming material: water=100:3:10:0.3:0.2:1500, the silicon source is with SiO
2Meter, the aluminium source is with Al
2O
3Meter, the platinum source is in Pt.Prepared collosol and gel is placed under 80 ° of C, the non-air tight condition dry 12 hours in 12 hours in ageing under 60 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 24 hours under the temperature of 160 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining removed template (TPAOH) and coupling pore-forming material (cetyl trimethylammonium bromide) in 15 hours, namely get the micropore-mesopore sial ZSM-5 molecular sieve that contains precious metal 0.5wt.%Pt.
Embodiment 7:
Use block polyoxyethylene polyoxypropylene ether (Pluronic F127) to be the micropore-mesopore ZSM-5 molecular sieve that contains precious metals pt of coupling pore-forming material synthesizing blender metal A l.
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (block polyoxyethylene polyoxypropylene ether Pluronic F127), silicon source (tetraethyl orthosilicate), aluminium source (aluminum isopropylate), alkali source (TPAOH) is stirred to the formation collosol and gel; Wherein mole forms the silicon source: aluminium source: alkali source: platinum source: coupling pore-forming material: water=100:3:10:0.3:0.2:1500, the silicon source is with SiO
2Meter, the aluminium source is with Al
2O
3Meter, the platinum source is in Pt.Prepared collosol and gel is placed under 80oC, the non-air tight condition dry 12 hours in 12 hours in ageing under 60 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 24 hours under the temperature of 160 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining removed template (TPAOH) and coupling pore-forming material (block polyoxyethylene polyoxypropylene ether Pluronic F127) in 15 hours, namely get the micropore-mesopore sial ZSM-5 molecular sieve that contains precious metal 0.5wt.%Pt.
Embodiment 8:
Use glucose to be the micropore-mesopore ZSM-5 molecular sieve that contains precious metals pt of coupling pore-forming material synthesizing blender metal A l.
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (glucose), silicon source (tetraethyl orthosilicate), and aluminium source (aluminum isopropylate), alkali source (TPAOH) is stirred to the formation collosol and gel; Wherein mole forms the silicon source: aluminium source: alkali source: platinum source: coupling pore-forming material: water=100:3:10:0.3:0.2:1500, the silicon source is with SiO
2Meter, the aluminium source is with Al
2O
3Meter, the platinum source is in Pt.Prepared collosol and gel is placed under 80 ° of C, the non-air tight condition dry 12 hours in 12 hours in ageing under 60 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 24 hours under the temperature of 160 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining removed template (TPAOH) and coupling pore-forming material (glucose) in 15 hours, namely get the micropore-mesopore sial ZSM-5 molecular sieve that contains precious metal 0.5wt.%Pt.
Embodiment 9: the synthetic micropore-mesopore pure silicon beta molecular sieve that contains precious metals pt
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (polyvinylpyrrolidone), silicon source (tetraethyl orthosilicate), alkali source (tetraethyl ammonium hydroxide: TEAOH), be stirred to the formation collosol and gel; Wherein mole forms the silicon source: alkali source: platinum source: coupling pore-forming material: water=100:30:0.3:0.2:1000, the silicon source is with SiO
2Meter, the platinum source is in Pt.Prepared collosol and gel is placed under 100 ° of C, the non-air tight condition dry 12 hours in 12 hours in ageing under 25 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 5 days under the temperature of 140 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining removed template (TPAOH) and coupling pore-forming material (glucose) in 15 hours, namely get the micropore-mesopore pure silicon beta molecular sieve that contains precious metal 0.5wt.%Pt.
Embodiment 10: the micropore-mesopore beta molecular sieve that contains precious metals pt of synthesizing blender metal A l
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (polyvinylpyrrolidone), silicon source (tetraethyl orthosilicate), aluminium source (aluminum isopropylate), alkali source (tetraethyl ammonium hydroxide: TEAOH), be stirred to the formation collosol and gel; Wherein mole forms the silicon source: aluminium source: alkali source: platinum source: coupling pore-forming material: water=100:5:30:0.3:0.2:1000, the silicon source is with SiO
2Meter, the aluminium source is with Al
2O
3Meter, the platinum source is in Pt.Prepared collosol and gel is placed under 100 ° of C, the non-air tight condition dry 12 hours in 12 hours in ageing under 25 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 5 days under the temperature of 140 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining removed template (tetraethyl ammonium hydroxide) and coupling pore-forming material (polyvinylpyrrolidone) in 15 hours, namely get the micropore-mesopore sial beta molecular sieve that contains precious metal 0.5wt.%Pt.
Embodiment 11: the micropore-mesopore beta molecular sieve that contains precious metals pt of synthesizing blender metal Ti
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (polyvinylpyrrolidone), silicon source (tetraethyl orthosilicate), aluminium source (aluminum isopropylate), alkali source (tetraethyl ammonium hydroxide: TEAOH), be stirred to the formation collosol and gel; Wherein mole forms the silicon source: aluminium source: alkali source: platinum source: coupling pore-forming material: water=100:2:30:0.3:0.2:1000, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the platinum source is in Pt.Prepared collosol and gel is placed under 100 ° of C, the non-air tight condition dry 12 hours in 12 hours in ageing under 25 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 5 days under the temperature of 140 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining removed template (tetraethyl ammonium hydroxide) and coupling pore-forming material (polyvinylpyrrolidone) in 15 hours, namely get the micropore-mesopore titanium silicon beta molecular sieve that contains precious metal 0.5wt%Pt.
Embodiment 12: the micropore-mesopore X(FAU type that contains precious metals pt of synthesizing blender metal A l) molecular sieve
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (polyvinylpyrrolidone), silicon source (tetraethyl orthosilicate), and aluminium source (aluminum nitrate), alkali source (sodium hydroxide) is stirred to the formation collosol and gel; Wherein mole forms the silicon source: aluminium source: alkali source: platinum source: coupling pore-forming material: water=100:25:20:0.2:0.2:1000, the silicon source is with SiO
2Meter, the aluminium source is with Al
2O
3Meter, alkali source is with Na
2The O meter, the platinum source is in Pt.Prepared collosol and gel is placed under 40 ° of C, the non-air tight condition dry 12 hours in 2 hours in ageing under 25 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 1 day under the temperature of 110 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining remove coupling pore-forming material (polyvinylpyrrolidone), namely get the micropore-mesopore X molecular sieve that contains precious metal 0.5wt.%Pt of doping metals Al.
Embodiment 13: the micropore-mesopore NaA(LTA type that contains precious metals pt of synthesizing blender metal A l) molecular sieve
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (polyvinylpyrrolidone), silicon source (tetraethyl orthosilicate), and aluminium source (sodium metaaluminate), alkali source (sodium hydroxide) is stirred to the formation collosol and gel; Wherein mole forms the silicon source: aluminium source: alkali source: platinum source: coupling pore-forming material: water=100:10:40:0.3:5:1000, the silicon source is with SiO
2Meter, the aluminium source is with Al
2O
3Meter, alkali source is with Na
2The O meter, the platinum source is in Pt.Prepared collosol and gel is placed under 40 ° of C dry 24 hours in 12 hours in ageing under 25 ° of C obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 3 days under the temperature of 110 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining remove coupling pore-forming material (polyvinylpyrrolidone), namely get the micropore-mesopore NaA molecular sieve that contains precious metal 0.5wt.%Pt of doping metals Al.
Embodiment 14: the micropore-mesopore L that contains precious metals pt (LTL type) molecular sieve of synthesizing blender metal A l
Synthesizing according to document Chem.Mater.2000, described in 12, the 1622-1627. of Pt nanoparticle.Synthetic particle through precipitation, centrifugal, in water, again be dispersed into 3 * 10
-3The solution of mol/L.
Under 40 ° of C water bath condition, in the aqueous solution of noble metal nano particles, add successively coupling pore-forming material (polyvinylpyrrolidone), silicon source (water glass), and aluminium source (sodium metaaluminate), alkali source (sodium hydroxide) is stirred to the formation collosol and gel; Wherein mole forms the silicon source: aluminium source: alkali source: platinum source: coupling pore-forming material: water=100:10:25:0.3:0.2:1500, the silicon source is with SiO
2Meter, the aluminium source is with Al
2O
3Meter, alkali source is with Na
2The O meter, the platinum source is in Pt.Prepared collosol and gel is placed under 40 ° of C, the non-air tight condition dry 24 hours in 12 hours in ageing under 25 ° of C, the air tight condition obtains dried glue.Then transfer in the crucible, crucible is placed with the upper strata in the teflon-lined stainless steel cauldron, lower floor is paved with water.The method that changes (SAC) by steam auxiliary phase crystallization 3 days under the temperature of 110 ° of C.With crystallization product through water with ethanol repeatedly washs and under 100 ° of C dry 12 hours.At last in air under 550 ° of C high temperature calcining remove coupling pore-forming material (polyvinylpyrrolidone), namely get the micropore-mesopore L molecular sieve that contains precious metal 0.5wt.%Pt of doping metals Al.
The above, it only is several case study on implementation of the present invention, be not that the present invention is done any pro forma restriction, although the present invention discloses as above with better case study on implementation, yet be not to limit the present invention, any those skilled in the art are not within breaking away from the technical solution of the present invention scope, when the structure that can utilize above-mentioned announcement and technology contents are made a little change or be modified to the equivalent case study on implementation of equivalent variations.But every content that does not break away from technical solution of the present invention, any simple modification, equivalent variations and modification according to technical spirit of the present invention is done above case study on implementation all still belong in the technical solution of the present invention scope.
Claims (9)
1. micropore-mesopore molecular screen material that contains precious metal, it is characterized in that: this molecular screen material has the aperture simultaneously less than the micropore canals of 2nm and the aperture mesopore orbit at 2～50nm, and its skeleton consists of the silica-based molecular screen material that silica-based molecular screen material that pure silicon molecular screen material, Al mix or Ti mix; Active noble metals nanoparticle high dispersing is in mesopore orbit; SiO
2, Al
2O
3Or TiO
2, noble metal source mol ratio be 100:0～25:0.1～5.
2. a kind of micropore-mesopore molecular screen material that contains precious metal as claimed in claim 1, it is characterized in that: the active noble metals nanoparticle is the alloy of one or more precious metals in the precious metals such as Pt, Ru, Rh, Pd, Re, Os, Ir, Ag and Au; Molecular sieve is MFI, FAU, BEA, MOR, LTA, LTL, SOD, GIS, OFF, ZSM-2, MTN or AEL molecular sieve.
3. in-situ preparation method that contains the micropore-mesopore molecular sieve of precious metal, its step is as follows:
1) under water bath condition, in the aqueous solution of noble metal nano particles, add successively the coupling pore-forming material, the silicon source, aluminium source or titanium source, alkali source is stirred to the formation collosol and gel; Wherein the mol ratio of silicon source, aluminium source or titanium source, alkali source, noble metal source, coupling pore-forming material, water is 100:0～25:10～40:0.1～5:0.1～5:500～1500, and the silicon source is with SiO
2Meter, the aluminium source is with Al
2O
3Meter, the titanium source is with TiO
2Meter, noble metal source is in precious metal simple substance;
2) with the collosol and gel ageing;
3) the collosol and gel drying after the ageing is obtained dried glue;
4) dried glue is transferred in the reactor, by the method that the steam auxiliary phase changes, carried out crystallization;
5) crystallization product is repeatedly washed, dries through water and ethanol, template is removed in the final high temperature calcining, thereby prepares the micropore-mesopore molecular sieve that contains precious metal.
4. a kind of in-situ preparation method that contains the micropore-mesopore molecular sieve of precious metal as claimed in claim 3, it is characterized in that: the bath temperature described in the step 1) is 25 ° of C～80 ° C; Step 2) Aging Temperature described in is 25 ° of C～100 ° C, and digestion time is 2～24 hours; Drying temperature described in the step 3) is 25 ° of C～100 ° C, and be 0.5～24 hour time of drying; The temperature rise rate of calcining is 1～2 ° of C/min, and calcining temperature is 500～650 ° of C, and calcination time is 6～24 hours.
5. a kind of in-situ preparation method that contains the micropore-mesopore molecular sieve of precious metal as claimed in claim 3, it is characterized in that: the noble metal nano particles described in the step 1) is one or more among Pt, Ru, Rh, Pd, Re, Os, Ir, Ag, the Au; Silicon source described in the step 1) is methyl silicate, tetraethoxy, white carbon black, water glass or silicon sol; Described aluminium source is pseudo-boehmite, aluminum isopropylate, aluminum nitrate, Tai-Ace S 150, aluminium sesquioxide, aluminum chloride or aluminium hydroxide; Described titanium source is tetra-n-butyl titanate, titanium isopropylate, tetraethyl titanate, titanium tetrachloride, titanium sulfate or titanium valve; Described alkali source is sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, urea, quaternary ammonium hydroxide compounds, fat amine compound or alcamine compound; Molecular sieve is MFI, FAU, BEA, MOR, LTA, LTL, SOD, GIS, OFF, ZSM-2, MTN or AEL molecular sieve; The coupling pore-forming material is polymkeric substance or tensio-active agent.
6. a kind of in-situ preparation method that contains the micropore-mesopore molecular sieve of precious metal as claimed in claim 5, it is characterized in that: the general formula of quaternary ammonium hydroxide compounds is (R
1)
4NOH, R
1For having the alkyl of 1～4 carbon atom; The general formula of fat amine compound is R
2(NH
2)
n, R
2Be selected from alkyl or alkylidene group with 1～6 carbon atom, n=1 or 2; The general formula of alcamine compound is (HOR
3)
mNH
(3-m), R
3Be selected from the alkyl with 1～4 carbon atom, m=1,2 or 3.
7. a kind of in-situ preparation method that contains the micropore-mesopore molecular sieve of precious metal as claimed in claim 5, it is characterized in that: polymkeric substance is glucose, cyclodextrin, polybenzimidazole, chitosan, polypropylene, polyoxyethylene glycol, polystyrene, polyvinyl chloride, polyethylene or methylcellulose gum, or the pyrrolidone of above-mentioned polymkeric substance, vinyl alcohol, ether, pyrimidine derivatives; Tensio-active agent is anion surfactant, cats product or nonionogenic tenside.
8. a kind of in-situ preparation method that contains the micropore-mesopore molecular sieve of precious metal as claimed in claim 7, it is characterized in that: anion surfactant is soap, sulfuric acid, phosphate ester salt, alkylbenzene sulfonate, sulfonated α-olefin, alkylsulfonate, alpha-sulfo monocarboxylate, lipid acid sulfoalkyl ester, sulphosuccinates, sulfonated alkyl naphathalene, sulfonated petro-leum, sulfonated lignin or alkyl glyceryl ether sulfonate; Cats product is fatty amines quaternary cationics or ring-type cats product; Nonionogenic tenside is fatty alcohol-polyoxyethylene ether, block polyoxyethylene polyoxypropylene ether, alkylol amide, polyol ester class, tween series, sapn is serial or the fluoride and carbon series tensio-active agent.
9. claim 1 or the 2 described a kind of application of micropore-mesopore molecular screen material in the p-NP catalytic reduction that contain precious metal.
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